EP3822395A1 - Nanowires network - Google Patents

Nanowires network Download PDF

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Publication number
EP3822395A1
EP3822395A1 EP19382996.7A EP19382996A EP3822395A1 EP 3822395 A1 EP3822395 A1 EP 3822395A1 EP 19382996 A EP19382996 A EP 19382996A EP 3822395 A1 EP3822395 A1 EP 3822395A1
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Prior art keywords
nanowires
network
gas flow
present
reaction vessel
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EP19382996.7A
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German (de)
English (en)
French (fr)
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Juan José VILATELA GARCÍA
Richard Santiago SCHÄUFELE
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Fundacion Imdea Materiales
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Fundacion Imdea Materiales
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Priority to EP19382996.7A priority Critical patent/EP3822395A1/en
Priority to KR1020227019425A priority patent/KR20220098208A/ko
Priority to PCT/EP2020/081963 priority patent/WO2021094485A1/en
Priority to MX2022005798A priority patent/MX2022005798A/es
Priority to IL292815A priority patent/IL292815A/en
Priority to CA3161140A priority patent/CA3161140A1/en
Priority to CN202080079654.1A priority patent/CN114901874B/zh
Priority to EP20803212.8A priority patent/EP4058622A1/en
Priority to AU2020382885A priority patent/AU2020382885A1/en
Priority to US17/755,937 priority patent/US20220389614A1/en
Priority to JP2022528064A priority patent/JP2023502383A/ja
Publication of EP3822395A1 publication Critical patent/EP3822395A1/en
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
    • C30B29/62—Whiskers or needles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • C30B11/04—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method adding crystallising materials or reactants forming it in situ to the melt
    • C30B11/08—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method adding crystallising materials or reactants forming it in situ to the melt every component of the crystal composition being added during the crystallisation
    • C30B11/12—Vaporous components, e.g. vapour-liquid-solid-growth
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • C30B11/14—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method characterised by the seed, e.g. its crystallographic orientation
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/005—Growth of whiskers or needles
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
    • C30B29/06—Silicon
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
    • C30B29/08—Germanium
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape

Definitions

  • the present invention relates to the synthesis of a network of nanowires. More specifically, the present invention relates to a process for preparing said network of nanowires.
  • Nanowires comprised of nanowires present advantages over materials made of larger building blocks.
  • nanowires are mechanically flexible due to their nanoscale dimensions and have a reduced amount of defects in comparison with bulk materials. They also display various optoelectronic properties resulting from their small size and one-dimensional morphology. Consequently, some of the properties of the nanowires networks depend on the characteristics of the nanowires. Thus a high degree of control over the nanowires' crystalline quality, morphology and size distribution is needed.
  • Heurlin, M. et al. Heurlin, M. et al. Nature volume 492, pages 90-94, 2012 ) discloses an aerosol-based nanowire growth method (aerotaxy method) wherein catalytic size-selected Au aerosol particles induce nucleation and growth of GaAs nanowires at a growth rate of about 1 micrometre per second.
  • the effectivity of aerotaxy method has only been demonstrated for the synthesis of GaAs (GaAsNWs), P-, Zn- and Sn-doped GaAsNWs nanowires and InP nanoparticles ( Magnusson, M. H. et al. Frontiers of Physics, 9(3), 398-418, 2014 ).
  • WO2013176619 (A1 ) describes a gas phase nanowire synthesis method that claims to be able to grow individual silicon nanowires followed by a subsequent step of spraying said nanowires through a spray nozzle followed by their deposition onto a substrate to form a network of nanowires.
  • the spraying and deposition step may be performed right after the synthesis of nanowires or after the storage of said nanowires in a reservoir.
  • two-step methods for synthesis of nanowire networks lead to nanowires shortening and therefore to degraded materials.
  • the nanowires forming the network are not permanently entangled or associated and need to be deposited on a supporting substrate to generate self-standing materials.
  • the inventors of the present invention have found a one-step method for producing self-standing networks of nanowires with good mechanical properties, such as good flexibility in bending, and wherein the nanowires have high aspect ratios.
  • the discovery of self-standing networks of nanowires that are also flexible represents a breakthrough since they allow post-production manipulation of the nanowire network as an engineering material, rather than as a powder or filler which typically undergo degradation and/or nanowire shortening during dispersion upon processing.
  • the method of the present invention allows the production of networks of nanowires in large amounts and at high rates. This approach is of great importance for a large variety of applications of networks of nanowires in various technological fields, since it solves the current limitations of the prior art.
  • the method of the present invention is based on aerosol technology and has the potential of being scaled up to large volumes, while maintaining a high level of control over the process.
  • the invention is directed to a method for preparing a network of nanowires comprising the steps of:
  • the invention is directed to a network of nanowires obtainable by the method as defined above.
  • the present invention is directed to a nonwoven material comprising the network of nanowires of the present invention.
  • the present invention is directed to the use of the network of nanowires of the present invention, in electronic devices, micromechanical systems, optoelectronic devices, wearable devices, insulators, sensors, electrodes, catalysis, structural elements, batteries, flexible devices and transparent devices.
  • the present invention is directed to the use of the nonwoven materials of the present invention, in electronic devices, micromechanical systems, optoelectronic devices, wearable devices, insulators, sensors, electrodes, catalysis, structural elements, batteries, flexible devices and transparent devices.
  • the invention is directed to a method for preparing a network of nanowires comprising the steps of:
  • the method for preparing a network of nanowires may comprise a further step of transforming the network of nanowires into fibers, yarns or fabrics.
  • the method for preparing a network of nanowires comprises a further step of collecting the network of nanowires; particularly by spinning and winding the network of nanowires (as a yarn or a fabric) on a bobbin.
  • the method for preparing a network of nanowires of the present invention comprises a step (i) of providing a first gas flow to a reaction vessel; wherein said first gas flow comprises at least one precursor compound comprising at least one element selected from Si, Ge, Al, B, Cu, Zn, Cd, Al, Ga, In, As, Sb, Nb, Ni, Ti, Se, Ta, Pt, Cu, Mo, W, C and Te.
  • the first gas flow further comprises H 2 .
  • the first gas flow further comprises an inert gas, particularly N 2 .
  • the step (i) of the method of the present invention provides a first gas flow to a reaction vessel wherein said first gas flow comprises at least one precursor compound.
  • the at least one precursor compound of the method of the present invention comprises at least one element selected from Si, Ge, Al, B, Cu, Zn, Cd, Al, Ga, In, As, Sb, Nb, Ni, Ti, Se, Ta, Pt, Cu, Mo, W and Te; particularly Si, Ge, In, Ga, Se and Te; more particularly Si and Ge; even more particularly Si.
  • the at least one precursor compound is one precursor compound.
  • the at least one precursor compound may be in solid or liquid form (i.e. aerosolized in the first gas flow of the method of the present invention) or in gas form.
  • the at least one precursor compound is in gas form.
  • the at least one precursor compound of the method of the present invention is a metallic hydride or an organometallic compound.
  • Precursors of the present invention include but are not limited to silane derivates such as (3-Aminopropyl)triethoxysilane, N-sec-Butyl(trimethylsilyl)amine, chloropentamethyldisilane, tetramethylsilane, silicon tetrabromide, silicon tetrachloride, tris(tert-butoxy)silanol, SiH 4 , tetramethylgermanium, triethylgermanium hydride, triphenylgermanium hydride, triphenylgermanium hydride, tetramethylgermanium, tributylgermanium hydride, triethylgermanium hydride, triphenylgermanium hydride, trimethylindium (TMin), trimethylindium (TEIN), trimethylgallium (TM
  • the at least one precursor compound is a metallic hydride, particularly SiH 4 .
  • the at least one precursor compound is an organometallic compound.
  • the first gas flow comprises more than one precursor compound.
  • the first gas flow comprises a first precursor compound and additional precursor compounds.
  • the additional precursor compounds may be used as dopants of the nanowire network (in less amount that the main precursor compound). Suitable dopants depend on the nanowire material being doped.
  • the at least one precursor compound of the present invention is provided to the reaction vessel of the present invention at a rate of at least 0.01 mol/h; preferably at a rate of at least 0.05 mol/h.
  • the method for preparing a network of nanowires of the present invention comprises a step (ii) of providing a second gas flow to the reaction vessel, said second glass flow comprising metallic catalyst particles; so as the first and second gas flows are mixed in the reaction vessel to form a gas flow mixture.
  • the second gas flow of the method of the present invention further comprises an inert gas, preferably N 2 .
  • the second gas flow of the method of the present invention further comprises H 2 .
  • the method for preparing a network of nanowires of the present invention comprises a step (ii) of providing a second gas flow comprising metallic catalyst particles.
  • the metallic catalyst particles of the method of the present invention comprise one or more element selected from Au, Ag, Cu, Fe, Ni, Ga, Co, Pt, In and Al; particularly comprise one or more element selected from Au, Ag and Cu; more particularly comprise one or more element selected from Au and Ag; even more particularly comprise Au.
  • the metallic catalytic particles may consist of a single element, or a combination (e.g. alloy) of two or more elements.
  • the metallic catalyst particles may be in the second gas flow as solid particles or as liquid particles; preferably as solid particles.
  • the metallic catalyst particles of the method of the present invention further comprise one or more additional elements selected from group 16 elements to control and/or enhance the growth of nanowires.
  • This additional elements are particularly selected from oxygen, sulfur, selenium, tellurium, and polonium; more particularly selected from S, Se, Te and O.
  • the metallic catalyst particles consist of one element selected from Au, Ag, Cu, Fe, Ni, Ga, Co, Pt, In and Al; particularly consist of one element selected from Au, Ag and Cu; more particularly consist of one element selected from Au and Ag; even more particularly consist of Au.
  • the metallic catalyst particles have an averaged diameter of between 0.1 and 100 nm; preferably of between 1 and 30 nm.
  • the average diameters of the metallic catalyst particles of the present invention may be calculated from an average of the values obtained by measuring the diameters of more than 100 metallic catalyst particles using electronic microscopy micrographs or from the size distribution obtained from different aerosol measuring technics such as from a Differential Mobility Particle Sizer (DMA).
  • DMA Differential Mobility Particle Sizer
  • the metallic catalyst particles may be provided without electrical charge or the metallic catalytic particles may be given a charge.
  • the metallic catalyst particles may be provided to the reaction vessel in the form of an aerosol generated by an upstream aerosol generator.
  • the metallic catalyst particles may be formed in-situ by providing a precursor compound; preferably a gaseous precursor compound.
  • the metallic catalyst particles are provided in the form of an aerosol.
  • the metallic catalyst particles enter the reaction vessel at a rate of at least 1 x 10 -5 g/h; preferably of at least 1 x 10 -4 g/h; more preferably of at least 2 x 10 -4 g/h; even more preferably of about more preferably of at least 2.7 x 10 -4 g/h.
  • the gas flow mixture of the method of the present invention is generated when the first and the second gas flow are in contact in the reaction vessel.
  • Means for mixture may be used to mix the flows to form a gas flow mixture. Pressure and flow rates might be adjusted if necessary to ensure a proper mixture of the first and second flow to form a gas flow mixture.
  • the gas flow mixture circulates in the reaction vessel at a rate of at least 60 I/h; preferably at least 120 I/h.
  • the gas flow mixture has a residence time in the reaction vessel of less than 100 seconds; particularly of between 10 and 80 seconds; more particularly of between 20 and 60 seconds; even more particularly of about 40 seconds.
  • sheath flows may be introduced in the reaction vessel of the present invention.
  • Sheath flows include, but are not limited to, nitrogen, hydrogen and noble gases such as helium and argon.
  • the at least one precursor compound is in the gas flow mixture in a mole fraction (xi) of at least 0.005.
  • the at least one precursor compound is in the gas flow mixture in a mole fraction of at least 0.006; particularly of at least 0.01; more particularly of at least 0.015; even more particularly of between 0.01 and 0.5; preferably of about 0.02.
  • the mole fraction is expressed as the amount of a constituent (in moles), divided by the total amount of all constituents (also expressed in moles).
  • the at least one precursor compound of the present invention is in the gas flow mixture in a concentration of at least 0.1 ⁇ 10 -4 mol/l; particularly in a concentration of at least 1 ⁇ 10 -4 mol/l; more particularly in a concentration of at least 1.5 ⁇ 10 -4 mol/l; even more particularly of at least 2 ⁇ 10 -4 mol/l.
  • the gas flow mixture comprises H 2
  • the reaction vessel used in the process of the present invention is a gas reaction vessel; preferably a cylindrical reaction vessel; more preferably a metallic cylindrical reaction vessel; even more preferably a stainless steel cylindrical reaction vessel such as a tube.
  • the temperature inside the reaction vessel is homogeneous; in particular is homogeneous within 50 degrees along the reactor tube, more particularly is homogeneous over 80 cm from the hot zone.
  • the temperature inside the reaction vessel ranges from 200 to 800°C; this temperature range allows the precursor compound to decompose.
  • the temperature ranges from 300 to 700°C; more preferably from 400 to 650°C; even more preferably is about 600°C.
  • the pressure inside the reaction vessel is about 1 atm.
  • the at least one precursor compound decomposes under the temperature conditions inside the reaction vessel and grows on the metallic catalyst particles by vapor liquid-solid (VLS) and/or chemical vapor deposition (CVD) to form a network of nanowires.
  • VLS vapor liquid-solid
  • CVD chemical vapor deposition
  • the nanowires grow while being in the gas flow mixture (i.e. they are aerosolized).
  • the at least one precursor compound decomposes under the temperature conditions inside the reaction vessel and grows on the metallic catalyst particles by floating catalyst chemical vapor deposition (CVD) to form a network of nanowires.
  • one or more sheath flows may be introduced in the reaction vessel.
  • said one or more sheath flows might be introduced between the gas flow mixture and the walls of the reaction vessel.
  • the nanowires can be grown in the axial or radial direction, or in a combination of the two growth modes.
  • Nanowire growth may be initiated by catalytic decomposition of the at least one precursor compound on the surface of the metallic catalyst particles and nucleation of the nanowire on the surface of the metallic catalytic particles. After nucleation, the nanowire may grow directionally and form an elongated object, i.e. a nanowire. Growth may occur via vapor liquid-solid (VLS) and/or chemical vapor deposition (CVD). At the same time, the nanowires reach a critical concentration and aggregate to form a network of nanowires in the reaction vessel.
  • the method of the present invention is a continuous aggregated method.
  • the gas mixture flows through the reactor carrying metallic catalytic particles and the nanowire network flows through the reaction vessel length.
  • CVD chemical vapor deposition
  • Said catalyst particle may be suspended in the gas phase, commonly referred to as floating catalyst.
  • Said particles may be in molten or solid state and may include additional elements to control and/or enhance growth of nanowires as described herein above. This additional elements include group 16 elements, such as S, Se, Te, or oxygen.
  • Said precursors may also partially decompose on the surface of the reactor.
  • the method for preparing a network of nanowires of the present invention is performed under an aerogelation parameter of at least 1 ⁇ 10 -7 ; particularly under an aerogelation parameter of at least 1 ⁇ 10 -6 ; more particularly under an aerogelation parameter of at least 2 ⁇ 10 -6 .
  • the expression "aerogelation parameter” is understood as the product of the average aspect ratio of the nanowires (length/diameter) and the volumetric concentration (vc (volume of nanowires/volume of the reactor)).
  • VLS vapor-liquid-solid
  • a gas i.e. the at least one precursor compound on gas phase
  • a liquid catalyst particle which can rapidly adsorb a vapor to supersaturation levels, and from which crystal growth can occur from nucleated seeds at the gas-liquid-solid interface.
  • a nanowire network of the present invention is formed while being in the gas flow mixture (in the reaction vessel).
  • the network of nanowires of the present invention is generated as a continuous process.
  • the network of nanowires may be discretely generated.
  • the network of nanowires of the present invention is continuously generated.
  • the network of nanowires of the present invention is generated at a rate of at least 0.01 g/h; preferably at a rate of at least 0.02 g/h; more preferably at a rate of at least 0.05 g/h; even more preferably at a rate of about 0.1 g/h.
  • the network of nanowires of the present invention is generated at a rate of between 0.01 g/h and 10 g/h; preferably at a rate of between 0.02 g/h and 5 g/h; more preferably at a rate of between 0.05 g/h and 1 g/h; even more preferably at a rate of at between 0.09 g/h and 1 g/h.
  • An aspect of the present invention is directed to a network of nanowires obtainable by the method of the present invention in any of its particular embodiments.
  • the network of nanowires is self-standing.
  • self-standing refers to a structure that is not supported by other objects or structures, such as a substrate.
  • the nanowires of the network of the present invention are aggregated; particularly are strongly aggregated; particularly they are strongly aggregated by secondary forces such as van der Waals forces, permanent dipoles, hydrogen bonds and/or covalent bonds, entanglements and other forms of mechanical interlock.
  • strongly aggregated in the context of the present invention it is implied that the materials forms a solid object and that the nanowires that comprise the network cannot be easily dispersed without recourse to sonication, stirring, cutting or similar methods.
  • the network of nanowires of the present invention is a continuous network.
  • a continuous network is understood as a percolated non-discreet network.
  • the network of nanowires of the present invention is an aerogel, i.e. a solid material of low density; preferably of a density of below 10 -2 g/cm 3 ; preferably of below 10 -3 g/cm 3 ; more preferably of below 10 -4 g/cm 3 ; more preferably of below 10 -5 g/cm 3 .
  • the network of nanowires of the present invention has a density of at least 0.001 g/cm 3 ; particularly of at least 0.01 g/cm 3 .
  • the network of nanowires of the present invention is densified; particularly by mechanical methods, solvents addition methods, electromagnetic methods or similar methods.
  • the network of nanowires of the present invention has a density of at least 0.02 g/cm 3 ; preferably of at least 0.03 g/cm 3 ; more preferably of at least 0.04 g/cm 3 ; more preferably of at least 0.05 g/cm 3 .
  • the nanowires of the network of the present invention have an average aspect ratio (length/diameter) of at least 10; preferably of at least 100; more preferably at least 150; even more preferably at least 200.
  • the nanowires of the network of the present invention have an average aspect ratio (length/diameter) of between 1 and 1000; particularly of between 100 and 800; more particularly of between 100 and 700.
  • the average length of the nanowires of the network of the present invention is at least 1 micron; particularly at least 2 microns; preferably at least 5 microns; more preferably at least 10 microns.
  • the average length of the nanowires of the network of the present invention may be calculated from an average of the values obtained by measuring the lengths of more than 100 nanowires using electronic microscopy micrographs.
  • the network of nanowires of the present invention has a porosity below 99.9%; particularly below 99%; more particularly below 97%; even more particularly about 96%.
  • the network of nanowires of the present invention has a porosity below 90.0%.
  • the network of nanowires of the present invention has a porosity of between 99.9% and 30%; particularly of between 50% and 98%; more particularly of between 60% and 97%; even more particularly of about 96%.
  • the network of nanowires of the present invention has a porosity below 90.0%.
  • the nanowires of the network of nanowires of the present invention comprises at least one material selected from GaAs, InP, GaP, Ga x In 1_x As y P 1-y , Al x Ga 1-x As y P 1-y , GaSb, Ga x In 1-x As y Sb 1-y , GaN, InN, AIN, Al z Ga x In 1-x-z N, Si, SiC, Ge or Si x Ge 1-x , SiO x , TiO x , ZnO x , CdS, Ta x , MoS y , WS y , MoTe y , TaSe y , NbSe y , NiTe y , BN, Bi z Te y , BP, Cu, Pt and Ni x where 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1 and 0 ⁇ z ⁇ 1; preferably comprises Si, SiC, Ge or Si x Ge 1-x and SiO
  • the nanowires of the network of nanowires of the present invention consist of at least one material selected from GaAs, InP, GaP, Ga x In 1_x As y P 1-y , Al x Ga 1-x As y P 1-y , GaSb, Ga x In 1-x As y Sb 1-y , GaN, InN, AIN, Al z Ga x In 1-x-z N, Si, SiC, Ge or Si x Ge 1-x , SiO x , TiO x , ZnO x , CdS, Ta x , MoS y , WS y , MoTe y , TaSe y , NbSe y , NiTe y , BN, Bi z Te y , BP, Cu, Pt and Ni x where 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1 and 0 ⁇ z ⁇ 1; preferably comprises Si, SiC, Ge or Si x Ge 1-x and SiO
  • the network of nanowires of the present invention has a volumetric density of at least 0.01 g/cm 3 ; particularly of at least 0.05 g/cm 3 ; more particularly of at least 0.07 g/cm 3 ; even more particularly of at least 0.08 g/cm 3 preferably of at least 0.015 g/cm 3 ; more preferably of at least 0.02 g/cm 3 ; even more preferably about 0.1 g/cm 3. .
  • the network of nanowires of the present invention has a volumetric density of between 0.01 g/cm 3 and 0.2 g/cm 3 ; particularly between 0.05 g/cm 3 and 0.19 g/cm 3 .
  • the nanowires of the network of nanowires of the present invention are entangled; preferably are physically entangled.
  • the network of nanowires of the present invention is a network that comprises nanowires.
  • the network of nanowires of the present invention further comprise the metallic catalyst particles used in the method of the present invention.
  • the network of nanowires of the present invention further comprises coatings; particularly inorganic coatings.
  • the network of nanowires of the present invention can be chemically functionalized by gas-phase, liquid-phase, annealing or irradiation processes.
  • the nanowires of the network of nanowires of the present invention are predominantly aligned.
  • the nanowires of the network of nanowires of the present invention are drawn, stretched or subjected to electromagnetic or electrochemical methods to align the nanowires.
  • the network of nanowires of the present invention consist of nanowires.
  • Another aspect of the present invention is directed to a nonwoven material comprising the network of nanowires as defined in any of its particular embodiments.
  • the nonwoven material of the present invention comprises one or more layers of the network of nanowires of the present invention.
  • the nonwoven material of the present invention is a nonwoven fabric; preferably a unidirectional nonwoven fabric.
  • the nanowires of the network of nanowires of the nonwoven material of the present invention are oriented in a single direction; preferably in a single parallel direction.
  • the nonwoven material of the present invention is nonwoven fabric wherein the nanowires of the network of nanowires are oriented in a single direction; preferably in a single parallel direction.
  • the nonwoven material of the present invention is a yarn.
  • the nonwoven material of the present invention can be chemically functionalized by gas-phase, liquid-phase, annealing or irradiation processes that modify the surface chemistry of the nanowires.
  • Another aspect of the present invention is directed to the use of the network of nanowires of the present invention in electronic devices, micromechanical systems, optoelectronic devices, wearable devices, insulators, sensors, electrodes, catalysis, structural elements, batteries, flexible devices and transparent devices.
  • Another aspect of the present invention is directed to the use of the nonwoven material of the present invention in electronic devices, micromechanical systems, optoelectronic devices, wearable devices, insulators, sensors, electrodes, catalysis, structural elements, batteries, flexible devices and transparent devices.
  • a network of nanowires comprising silicon (Si) nanowires was produced by decomposition of a Si precursor in the presence of catalyst nanoparticles suspended in a gas stream inside a reaction vessel.
  • a first gas flow delivered a SiH 4 precursor (2 g/h) in a flow of H 2 (200 specific cubic centimeters per minute) to a reaction vessel.
  • a SiH 4 precursor (2 g/h) in a flow of H 2 (200 specific cubic centimeters per minute)
  • an aerosol of pre-synthesized catalyst gold nanoparticles in a N2 flow as main carrier gas (1 specific liters per minute) was introduced into the reaction vessel as a second gas flow. Then, the first and second flows mixed to form a gas flow mixture.
  • the SiH 4 precursor was in the gas flow mixture in a mole fraction of 0.02 (expressed as the amount of the precursor in moles, divided by the total amount of all constituents in the mixture also expressed in moles), and in a concentration of 2.4 ⁇ 10 -4 mol/l in the reaction vessel.
  • the reaction vessel used was a metallic reaction tube inside a tube furnace.
  • the Si precursor decomposed and associated with the catalyst particles.
  • Si nanowires grew rapidly inside the reaction vessel, also suspended in the gas stream.
  • the average length of the nanowires was at least 10 microns.
  • the nanowires entangled and interact among them in the reaction vessel, and formed a highly porous solid (network of nanowires), similar to a web or an aerogel (see Figure 3 ), associated through strong surface interactions among said nanowires.
  • the residence time in the reaction zone was less than 40 seconds.
  • the network material synthesized was collected by drawing it as a yarn or unidirectional non-woven fabric.
  • the network of nanowires material synthesized was free-standing (see Figure 4 ) and had sufficient mechanical stability to withstand handling under conditions relevant for further processing. As shown in Figure 5 , the obtained material is flexible enough to withstand a reversible bending to a curvature radius of a couple of milimetres (see Figure 5 ).
  • the network of nanowires presents a low volumetric density of 0.09 g/cm 3 and a porosity of about 96.0%.
  • the network of nanowires was produced at a rate over >1x10 -1 9 /h.

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KR1020227019425A KR20220098208A (ko) 2019-11-13 2020-11-12 나노와이어 네트워크
PCT/EP2020/081963 WO2021094485A1 (en) 2019-11-13 2020-11-12 Nanowires network
MX2022005798A MX2022005798A (es) 2019-11-13 2020-11-12 Red de nanohilos.
IL292815A IL292815A (en) 2019-11-13 2020-11-12 A network of nanocables
CA3161140A CA3161140A1 (en) 2019-11-13 2020-11-12 Nanowires network
CN202080079654.1A CN114901874B (zh) 2019-11-13 2020-11-12 纳米线网络
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US17/755,937 US20220389614A1 (en) 2019-11-13 2020-11-12 Nanowires network
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